High-sensitivity antibacterial composite leather as well as preparation method and application thereof

Abstract

The invention provides high-sensitivity antibacterial composite leather as well as a preparation method and application thereof, and belongs to the technical field of composite leather. The high-sensitivity antibacterial composite leather provided by the invention comprises a high-molecular complex functional phase and a polymer fiber structure phase, and the high-molecular complex functional phase and the polymer fiber structure phase are compounded into a high-molecular complex fiber and polymer fiber blended gray fabric; the fabric is a textile gray fabric made of polymer fibers and polymer compound composite spinning fibers, or a polymer fiber gray fabric loaded with a polymer compound; the high-molecular complex is formed by compounding a polyanionic polymer and a polycationic polymer. The composite leather has high sensitivity to the temperature and humidity of a human body, the perceptible temperature range is 30-40 DEG C, the humidity range is 30-90% of relative humidity, the glass-transition temperature of the composite leather is rapidly reduced (lt: 30 DEG C) at the environment temperature higher than the room temperature, and the composite leather has excellent skin-friendly performance and antibacterial performance.

Description

Technical Field

[0001] The invention relates to the technical field of composite leather, and in particular to a highly sensitive antibacterial composite leather and a preparation method and application thereof. Background Art

[0002] Antibacterial materials or fabrics have been widely used in socks, masks, underwear and other clothing items, which have improved people's living standards and convenience, significantly reduced the infection rate of pathogens, and improved public health. In addition to using antibiotics, antibacterial materials often contain cationic types, such as Cu 2+ , quaternary ammonium ions, Ag + Or photothermal properties to achieve sterilization. Positively charged antibacterial materials kill bacteria and viruses better by disrupting the bacterial membrane wall through positive charge. However, the non-affinity between cations and fabrics or polymers can lead to problems such as easy shedding. For example, commonly used polyester polymer materials are difficult to combine with metal ions, and are easy to fall off over a long period of time, resulting in reduced antibacterial properties and other problems, affecting service life. In addition, high concentrations of positively charged substances often produce unnecessary human toxicity, and their biological safety also needs to be considered.

[0003] Biosafety and biocompatibility are the key to the medical use of materials. Leather materials with antibacterial, antiviral and self-cleaning properties are important for improving the quality of healthy life. In the interaction between the human body and rehabilitation medical equipment, leather materials are direct contact points with the human body. During use, there are problems such as friction, rubbing, and sweat erosion. The antibacterial and biosafety evaluation of leather materials is important, especially when leather materials are used as biomedical devices, safety issues are particularly important. Summary of the invention

[0004] The purpose of the present invention is to provide a highly sensitive antibacterial composite leather and a preparation method and application thereof. The composite leather can sense human body temperature and humidity, improve the skin contact feel of the leather material, and has antibacterial properties, so as to be applied in automobile interiors, medical devices, and sports rehabilitation materials.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The present invention provides a highly sensitive antibacterial composite leather, comprising a high molecular complex functional phase and a polymer fiber structural phase; The composite form of the polymer complex functional phase and the polymer fiber structural phase is a blended grey fabric of polymer complex fiber and polymer fiber, or a textile grey fabric of polymer fiber and polymer complex composite spinning fiber, or a polymer fiber cloth grey fabric loaded with a polymer complex; The polymer complex in the polymer complex functional phase is formed by the fusion of a polyanionic polymer and a polycationic polymer.

[0006] Preferably, the polymer fibers in the polymer fiber structure phase include one or more of polyethylene terephthalate fibers, polycarbonate fibers, polyurethane fibers, nylon 6, nylon 66 and nylon 1010.

[0007] Preferably, the polyanionic polymer includes one or more of polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, sodium alginate and hyaluronic acid; the polycationic polymer includes one or more of polyethyleneimine, poly{[2-(methacryloxy)-ethyl]trimethylammonium salt}, chitosan and polydiallyldimethylammonium chloride; the mass ratio of the polyanionic polymer to the polycationic polymer is 1:50~50:1.

[0008] Preferably, the method for preparing the polymer fiber and high molecular weight compound composite spinning fiber comprises: impregnating the polymer fiber in a high molecular weight compound solution, pulling it, and then coagulating it in a coagulation bath to obtain a polymer fiber and high molecular weight compound composite spinning fiber with a skin-core structure.

[0009] Preferably, the method for preparing the polymer fiber cloth grey cloth loaded with a high molecular weight compound comprises: impregnating a grey cloth woven from polymer fibers in a high molecular weight compound solution, and then curing and shaping the grey cloth in a coagulation bath to obtain the polymer fiber cloth grey cloth loaded with a high molecular weight compound.

[0010] Preferably, the polymer complex solution contains salt ions; the salt ions include sodium ions or calcium ions, and the concentration of the salt ions in the polymer complex solution is 0.01~5mol / L; the pH value of the polymer complex solution is 1~5, and the concentration of the polymer complex in the polymer complex solution is 1~50wt.%.

[0011] Preferably, the coagulation bath contains auxiliary curing ions, which include one or more of sodium ions, calcium ions, iron ions and copper ions. The concentration of the auxiliary curing ions in the coagulation bath is 0.001-5 mol / L, and the pH value of the coagulation bath is 9-14.

[0012] Preferably, the mass ratio of the polymer complex functional phase to the polymer fiber structural phase is 1:100 to 100:1.

[0013] The present invention provides a method for preparing the highly sensitive antibacterial composite leather described in the above technical solution, comprising the following steps: The high molecular complex functional phase and the polymer fiber structural phase are compounded and post-processed to obtain a highly sensitive antibacterial composite leather.

[0014] The present invention provides the use of the highly sensitive antibacterial composite leather described in the above technical solution or the highly sensitive antibacterial composite leather prepared by the preparation method described in the above technical solution in automobile interiors, medical equipment or sports rehabilitation equipment.

[0015] The present invention provides a highly sensitive antibacterial composite leather, which uses a high molecular weight compound to construct the functional phase of the leather, has a high sensitivity to human body temperature and humidity and becomes soft and flexible, showing good skin-friendliness; the polycationic polymer in the high molecular weight compound has antibacterial and antibacterial properties, and can effectively kill and remove bacteria and viruses; a general polymer fiber structure phase is used as a leather support to give the leather good mechanical bearing capacity.

[0016] The present invention utilizes the compatibility of polycationic polymer and polyanion polymer at the molecular level. The high molecular complex formed by the electrostatic interaction between the two molecules has multifunctionality. The high molecular complex is used to construct the interactive multifunctional characteristics of leather materials, so that the leather has high sensitivity and high sensitivity to temperature and humidity changes. It can sense the temperature and humidity changes of the human body and adjust its mechanical flexibility adaptively. Under different temperature and humidity stimulation, the leather shows a specific flexibility, which improves the contact comfort between the human body and the leather. In addition, in the functional phase constructed by the high molecular complex, the polycationic polymer can destroy the bacterial membrane wall and kill bacteria, and has excellent antibacterial and antibacterial properties. It effectively kills and removes bacteria under long-term use, and the polycationic bactericidal system composed of high molecular polycationic polymers has a stable structure, so that the antibacterial performance of the leather material becomes stable and long-lasting, solving the problems of instability of traditional antibacterial materials such as quaternary ammonium salts and metal ions and the reduction of antibacterial performance and toxicity caused by easy shedding under long-term use. The multifunctional characteristic leather provided by the present invention provides a method and idea for preparing advanced composite leather materials, which can be used in the fields of automotive interior, medical equipment, rehabilitation equipment, etc.

[0017] The composite leather provided by the present invention has high sensitivity to human body temperature and humidity, with a sensing temperature range of 30-40°C and a humidity range of 30%-90% relative humidity. At an ambient temperature higher than room temperature (25°C, 30% relative humidity), its glass transition temperature decreases rapidly (<30°C), and it has excellent flexibility, thereby improving the comfort of contact between the leather and human skin. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of the fiber framework composition structure of the highly sensitive antibacterial leather of the present invention; Figure 2 Schematic diagram of the preparation process of polymer fiber with skin-core structure and high molecular weight composite spinning fiber; Figure 3 The chemical structures of the polyanionic polymer and the polycationic polymer used in preparing the polymer complex of the present invention; Figure 4 The dynamic mechanical analysis results of the composite leather prepared in Example 1, wherein (a) is the humidity-dependent dynamic mechanical analysis; (b) is the temperature-dependent dynamic mechanical analysis. DETAILED DESCRIPTION

[0019] like Figure 1 As shown, the present invention provides a highly sensitive antibacterial composite leather, comprising a polymer complex functional phase and a polymer fiber structural phase; The composite form of the polymer complex functional phase and the polymer fiber structural phase is a blended grey fabric of polymer complex fiber and polymer fiber, or a textile grey fabric of polymer fiber and polymer complex composite spinning fiber, or a polymer fiber cloth grey fabric loaded with a polymer complex; The polymer complex in the polymer complex functional phase is formed by the fusion of a polyanionic polymer and a polycationic polymer.

[0020] In the present invention, unless otherwise specified, the required reagents or materials are commercially available products well known to those skilled in the art.

[0021] In the present invention, the mass ratio of the polymer complex functional phase to the polymer fiber structural phase is preferably 1:100 to 100:1, more preferably 95:5.

[0022] In the present invention, the polymer complex functional phase is constructed by a polymer complex, which provides the leather with high perception properties (sensitive to temperature and humidity changes) and antibacterial properties; polymer fibers are used to construct the structural phase of the leather as the mechanical structure support of the leather.

[0023] In the highly sensitive antibacterial composite leather provided by the present invention, the polymer fibers in the polymer fiber structure phase preferably include one or more of polyethylene terephthalate fibers, polycarbonate fibers, polyurethane fibers, nylon 6, nylon 66 and nylon 1010; when the polymer fibers are two or more of the above, the present invention has no special limitation on the ratio of different types of polymer fibers, which can be adjusted according to actual needs.

[0024] The highly sensitive antibacterial composite leather provided by the present invention comprises a polymer complex functional phase, wherein the polymer complex in the polymer complex functional phase is formed by combining a polyanionic polymer and a polycationic polymer. The polyanionic polymer and the polycationic polymer are combined at the molecular level through electrostatic action.

[0025] In the present invention, the polyanionic polymer preferably includes one or more of polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, sodium alginate and hyaluronic acid; the polycationic polymer preferably includes one or more of polyethyleneimine, poly{[2-(methacryloxy)-ethyl]trimethylammonium salt}, chitosan and polydiallyldimethylammonium chloride (structural formula see Figure 3 ); When the polyanionic polymer or polycationic polymer is preferably two or more of the above, the present invention has no special limitation on the ratio of different types of polyanionic polymers or polycationic polymers, which can be adjusted according to actual needs.

[0026] In the present invention, the mass ratio of the polyanionic polymer to the polycationic polymer is preferably 1:50-50:1, more preferably 1-2:1-3.

[0027] In the present invention, when the composite form of the polymer complex functional phase and the polymer fiber structural phase is a blended grey fabric of polymer complex fiber and polymer fiber, it is preferred to use polymer complex fiber and polymer fiber to blend and manufacture the grey fabric, and the mass ratio of polymer complex fiber and polymer fiber during blending can reach the required ratio of polymer complex functional phase and polymer fiber structural phase in composite leather. The polymer complex fiber is preferably prepared according to the spinning method described in patent ZL201410083610.2 or ZL 201410797962.4. The present invention has no special limitation on the process of blended manufacture, and it can be carried out according to methods well known in the art.

[0028] In the present invention, when the composite form of the polymer complex functional phase and the polymer fiber structural phase is a textile grey fabric of polymer fiber and polymer complex composite spinning fiber, as Figure 2 As shown, the preparation method of the polymer fiber and high molecular weight complex composite spinning fiber preferably includes: soaking the polymer fiber in a high molecular weight complex solution, immersing it in a coagulation bath for coagulation and forming after pulling, and drying to obtain a polymer fiber and high molecular weight complex composite spinning fiber with a skin-core structure (the high molecular weight complex is the skin and the polymer fiber is the core), and the soaking time is preferably 1 to 30 minutes, more preferably 10 to 20 minutes; in the polymer fiber and high molecular weight complex composite spinning fiber, the mass ratio of the high molecular weight complex to the polymer fiber reaches the required ratio of the high molecular weight complex functional phase and the polymer fiber structural phase in the composite leather. The present invention does not specifically limit the process of weaving the polymer fiber and high molecular weight complex composite spinning fiber into a textile grey cloth, and it can be woven according to the process well known in the art.

[0029] The present invention has no particular limitation on the specific conditions of the pulling method, and the pulling process can be carried out according to the pulling process well known in the art.

[0030] In the present invention, when the composite mode of the polymer complex functional phase and the polymer fiber structural phase is a polymer fiber cloth grey cloth loaded with a polymer complex, the preparation method of the polymer fiber cloth grey cloth loaded with a polymer complex preferably comprises: soaking a polymer fiber woven grey cloth in a polymer complex solution, curing and forming in a coagulation bath, and obtaining a polymer fiber cloth grey cloth loaded with a polymer complex. The soaking time is preferably 1 to 30 min, more preferably 10 to 20 min, and further preferably 15 min, and the mass ratio of the polymer complex to the polymer fiber in the polymer fiber grey cloth loaded with a polymer complex reaches the required ratio of the polymer complex functional phase and the polymer fiber structural phase in the composite leather.

[0031] The present invention has no special limitation on the specific weaving method of the grey cloth woven from the polymer fibers. The fabric can be woven according to methods well known in the art, and there is no special limitation on the weaving mode.

[0032] In the present invention, the polymer complex solution contains salt ions; the salt ions include sodium ions or calcium ions, and the concentration of the salt ions in the polymer complex solution is preferably 0.01-5 mol / L, more preferably 0.5-3 mol / L, and further preferably 1-2 mol / L; the pH value of the polymer complex solution is preferably 1-5, more preferably 1-3, and the concentration of the polymer complex in the polymer complex solution is preferably 1-50 wt.%, more preferably 5-15 wt%. The present invention does not specifically limit the specific type of salt corresponding to the salt ions, and the corresponding water-soluble salts well known in the art can be used, and more preferably sodium chloride or calcium chloride.

[0033] The present invention utilizes salt ion concentration and pH regulation to control the solubility of the complex, and the salt ion is a polymer counter ion to help dissolve the complex.

[0034] In the present invention, the method for preparing the polymer complex solution is preferably to dissolve the polycationic polymer and the polyanionic polymer in a salt solution corresponding to the salt ions, stir and mix, and adjust the pH value to a desired value using commercially available hydrochloric acid to obtain the polymer complex solution.

[0035] In the present invention, the coagulation bath preferably contains auxiliary curing ions, and the auxiliary curing ions include one or more of sodium ions, calcium ions, iron ions and copper ions. The concentration of the auxiliary curing ions in the coagulation bath is preferably 0.001-5 mol / L, more preferably 0.01-0.5 mol / L, and further preferably 0.1-0.05 mol / L. The pH value of the coagulation bath is preferably 9-14, and more preferably 11-13. The present invention has no special limitation on the metal compound corresponding to the auxiliary curing ions, and the metal compound corresponding to the required pH can be used; the present invention preferably uses sodium hydroxide well known in the art to adjust the required pH value of the coagulation bath; in the embodiment of the present invention, the coagulation bath is specifically a sodium hydroxide aqueous solution.

[0036] The present invention provides a method for preparing the highly sensitive antibacterial composite leather described in the above technical solution, comprising the following steps: The high molecular complex functional phase and the polymer fiber structural phase are compounded and post-processed to obtain a highly sensitive antibacterial composite leather.

[0037] In the present invention, when the composite form of the polymer complex functional phase and the polymer fiber structural phase is a blended grey cloth of polymer complex fiber and polymer fiber, it is preferred to blend the polymer complex fiber and polymer fiber to obtain the grey cloth, and then obtain the highly sensitive antibacterial composite leather through post-processing.

[0038] In the present invention, when the composite form of the polymer complex functional phase and the polymer fiber structural phase is a textile grey cloth of polymer fiber and polymer complex composite spun fiber, it is preferred to composite spin the polymer fiber and the polymer complex to obtain skin-core structure fiber, then weave to obtain the grey cloth, and then post-process to obtain a highly sensitive antibacterial composite leather.

[0039] In the present invention, when the composite form of the polymer complex functional phase and the polymer fiber structural phase is that the polymer fiber cloth grey cloth is loaded with the polymer complex, it is preferred to impregnate and solidify the polymer fiber-based grey cloth with the polymer complex resin to form leather, and then obtain a highly sensitive antibacterial composite leather through post-processing.

[0040] In the present invention, the post-processing method preferably includes sanding or hot pressing.

[0041] The present invention has no particular limitation on the specific process of weaving and post-processing. The desired composite leather can be obtained by weaving according to the process well known in the art and actual needs.

[0042] The present invention provides the application of the highly sensitive antibacterial composite leather described in the above technical solution or the highly sensitive antibacterial composite leather prepared by the preparation method described in the above technical solution in automobile interior decoration, medical equipment or sports rehabilitation equipment. The present invention has no special limitation on the application method, and the application can be carried out according to methods well known in the art.

[0043] The composite leather provided by the present invention has the following characteristics: first, it can sense the temperature and humidity of the human body environment, and the electrostatic interaction between the molecules of the composite under the synergistic effect of temperature and humidity is dynamically regulated, the macroscopic physical properties change, and its mechanical and hydrophilic and hydrophobic properties change, thereby improving the comfort of skin contact; second, it has antibacterial properties, and the polycationic polymer in the composite can disrupt the bacterial membrane wall, kill bacteria, and show antibacterial properties. Specifically, the high-molecular composite is highly sensitive to the temperature and humidity environment of the human body. When the human body contacts the leather, the electrostatic interaction between the molecules in the composite under the synergistic effect of temperature and humidity dissociates, the molecular chain segments of the composite relax, and the leather surface becomes softer and skin-friendly, thereby improving the skin affinity of the leather surface. In addition, during the electrostatic dissociation process, the polycationic polymer in the composite contacts with bacteria, destroys the bacterial membrane wall, kills bacteria, and shows antibacterial properties. When it is restored to room temperature or normal state, the electrostatic interaction of the composite is formed, and the molecular chain segments of the composite tighten. This process can remove bacteria and prevent the infection of external bacteria.

[0044] In the present invention, the polymer composite is composed of two or more polymers that are bonded at the molecular level through non-covalent interactions such as hydrogen bonds and electrostatic interactions between molecular chains. There are abundant hydrogen bonds or electrostatic interactions between the molecular chains of the polymer. Hydrogen bonds or electrostatic interactions are a kind of dynamic non-covalent bonds that can be dynamically combined or destroyed under external stimuli, and exhibit different physical properties, such as mechanical properties, at the macroscopic level of the material.

[0045] The present invention uses a polymer compound to construct the functional phase of the leather, and utilizes the high sensitivity of the polymer compound to temperature and humidity to improve the skin-friendly performance of the leather material. Under the stimulation of temperature and humidity, the hydrogen bonds and electrostatic effects between molecules of the polymer compound are dynamically dissociated and reorganized, and its mechanical behavior becomes soft and soft, achieving a good skin-friendly effect. When it is restored to room temperature or normal state, the hydrogen bonds or electrostatic effects between molecules are recombined, so that the molecular chains are tightly bound, thereby blocking the invasion of bacteria. In addition, a polycationic polymer is introduced into the compound, and the cationic properties can disrupt the bacterial membrane or wall, kill bacteria, and simultaneously achieve an antibacterial and bactericidal effect. Cationic molecules (quaternary ammonium salts) antibacterial materials have a good killing effect on bacteria, but small quaternary ammonium salts are easy to fall off, thereby reducing the antibacterial performance of the material, and the antibacterial effect is unstable, and the detached quaternary ammonium salt molecules have a certain toxic effect on cells, which is harmful to the human body. The present invention uses a polycationic polymer to solve the above problems, and the polycationic polymer can form a compound with a negatively charged polymer, thereby showing more functionality.

[0046] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0047] Example 1

[0048] Commercially available polyethylene terephthalate fiber is used as the structural fiber, sodium alginate and polydiallyldimethylammonium chloride are used in a mass ratio of 1:1, and high molecular weight complex fiber is spun according to the method described in patent (ZL 201410083610.2). The structural fiber and the high molecular weight complex fiber are blended into mixed yarn, which is then spun into grey cloth to obtain a primary fabric. After the fabric is opened and sanded, the mass ratio of the high molecular weight complex functional phase to the polymer fiber structural phase is 95:5 to obtain a composite leather.

[0049] Performance Testing The composite leather prepared in Example 1 was tested using the temperature accessory and humidity accessory of a dynamic thermomechanical analyzer. The temperature was changed while the leather was kept dry, or the humidity was changed while the temperature was kept at 25° C., to observe the changes in its mechanical behavior.

[0050] Figure 4 The dynamic mechanical analysis results of the composite leather prepared in Example 1, wherein (a) is the humidity-dependent dynamic mechanical analysis, indicating that the composite leather has obvious mechanical relaxation at a humidity of 40%; (b) is the temperature-dependent dynamic mechanical analysis, indicating that the composite leather has obvious mechanical relaxation at 37°C, indicating that the composite leather is highly sensitive to temperature and humidity.

[0051] The composite leather prepared in this embodiment has obvious mechanical transformation behavior between 30-90% relative humidity and 30-40° C., and has high flexibility and skin affinity.

[0052] The test method is as follows: in a 6-well plate, the composite leather of Example 1 is spread flat on the bottom of the well plate, and then a bacterial culture solution (500 uL, 1× 10 5 CFU / mL), added bacterial suspension, co-incubated at room temperature, and the antibacterial effect was evaluated using the plate count method. The results showed that it had a significant antibacterial effect (>98%) against Escherichia coli and Staphylococcus aureus.

[0053] Example 2

[0054] Nylon 6 fiber was used as structural fiber, and sodium polyacrylate, chitosan and polyethyleneimine were used to prepare polymer complex functional fiber. Sodium polyacrylate, chitosan and polyethyleneimine were dissolved in a pH=1, 1 mol / L sodium chloride solution at a mass ratio of 2:1:1. The complex concentration in the formed polymer complex solution was 5wt.%. Nylon 6 fiber was immersed in the polymer complex solution. After 10 minutes of immersion, the fiber was pulled out by a pulling method. The nylon 6 fiber wall was adhered with a complex coating. Then, the fiber was immersed in a sodium hydroxide aqueous solution with a sodium ion concentration of 0.01 mol / L and pH=13. The fiber was collected, and its structure was a skin-core structure. The obtained fiber was woven into grey cloth, and then it was opened and sanded. The mass ratio of the polymer complex functional phase to the polymer fiber structural phase was 1:5 to obtain a composite leather.

[0055] Example 3

[0056] Commercially available polyethylene terephthalate fiber was used as the structural fiber grey cloth, and sodium polyacrylate and poly{[2-(methacryloxy)-ethyl]trimethylammonium salt} were dissolved in a pH=2, 1 mol / L calcium chloride solution at a mass ratio of 1:3. The formed polymer complex solution had a complex concentration of 5wt.%. The structural fiber grey cloth was soaked in the polymer complex solution. After soaking for 30 min, it was immersed in a sodium hydroxide aqueous solution with a sodium ion concentration of 0.05 mol / L and pH=13 for solidification. After being reduced and opened, and sanded, the mass ratio of the polymer complex functional phase to the polymer fiber structural phase was 1:3, and a composite leather was obtained.

[0057] The composite leather prepared in this embodiment has a high sensitivity to skin temperature and humidity, becomes softer during skin contact, and has a high skin-friendly effect. In addition, its antibacterial effect is >99%.

[0058] Example 4

[0059] Nylon 66 fiber is used as structural fiber, sodium polyacrylate, chitosan and polyethyleneimine are used in a mass ratio of 5:3:2, and high molecular weight complex fiber is spun according to the method described in patent (ZL 201410083610.2). The two fibers are blended to obtain a raw fabric, which is then opened and sanded. The mass ratio of the high molecular weight complex functional phase to the polymer fiber structural phase is 95:5, and a composite leather is obtained.

[0060] According to the testing method of Example 1, the composite leather prepared in this example has obvious mechanical transformation behavior between 25% and 80% relative humidity and 30 to 38°C, and has high flexibility and skin-friendliness; in addition, it has obvious antibacterial effect (>99%) against Escherichia coli and Staphylococcus aureus.

[0061] Example 5

[0062] Polyethylene terephthalate fiber is used as structural fiber, sodium polyacrylate and poly{[2-(methacryloxy)-ethyl]trimethylammonium salt} are dissolved in a pH=1, 1 mol / L sodium chloride solution at a mass ratio of 2:1, and the formed polymer complex solution has a complex concentration of 5wt.%. The polyethylene terephthalate fiber is immersed in the polymer complex solution for 15 minutes, and then drawn out. The polyethylene terephthalate fiber wall is adhered with a complex coating, and then immersed in a sodium hydroxide solution with a sodium ion concentration of 0.5 mol / L and a pH=13. The fiber is collected, and its structure is a skin-core structure. The obtained fiber is woven into a grey cloth, and after being reduced, opened and sanded, the mass ratio of the polymer complex functional phase to the polymer fiber structural phase is 1:10, and a composite leather is obtained.

[0063] Example 6

[0064] Commercially available nylon 66 fiber grey cloth was used as the structural phase, and sodium polymethacrylate and polyethyleneimine were dissolved in a pH=3, 1 mol / L sodium chloride solution at a mass ratio of 1:2. The concentration of the complex in the formed polymer complex solution was 15wt.%. The nylon 66 fiber grey cloth was soaked in the polymer complex solution for 30 minutes, and then immersed in a sodium hydroxide solution with a calcium ion concentration of 0.1 mol / L and pH=13 for curing. After reduced fiber opening and sanding, the mass ratio of the polymer complex functional phase to the polymer fiber structural phase was 1:7, and a composite leather was obtained.

[0065] The composite leather prepared in this embodiment is highly sensitive to skin temperature and humidity, becomes softer and softer during skin contact, and has a high skin-friendly effect. In addition, its antibacterial effect is >99%.

[0066] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A highly sensitive antibacterial composite leather, characterized in that: It includes a polymer complex functional phase and a polymer fiber structural phase; The composite form of the polymer complex functional phase and the polymer fiber structural phase is a blended grey fabric of polymer complex fiber and polymer fiber, or a textile grey fabric of polymer fiber and polymer complex composite spinning fiber, or a polymer fiber cloth grey fabric loaded with a polymer complex; The polymer complex in the polymer complex functional phase is formed by the fusion of a polyanionic polymer and a polycationic polymer.

2. The highly sensitive antibacterial composite leather according to claim 1, characterized in that: The polymer fibers in the polymer fiber structure phase include one or more of polyethylene terephthalate fibers, polycarbonate fibers, polyurethane fibers, nylon 6, nylon 66 and nylon 1010.

3. The highly sensitive antibacterial composite leather according to claim 1, characterized in that: The polyanionic polymer includes one or more of polyacrylic acid, sodium polyacrylate, polymethacrylic acid, sodium polymethacrylate, sodium alginate and hyaluronic acid; the polycationic polymer includes one or more of polyethyleneimine, poly{[2-(methacryloxy)-ethyl]trimethylammonium salt}, chitosan and polydiallyldimethylammonium chloride; the mass ratio of the polyanionic polymer to the polycationic polymer is 1:50~50:

1.

4. The highly sensitive antibacterial composite leather according to claim 1, characterized in that: The preparation method of the polymer fiber and high molecular compound composite spinning fiber comprises: impregnating the polymer fiber in a high molecular compound solution, pulling it, and then coagulating it in a coagulation bath to obtain a polymer fiber and high molecular compound composite spinning fiber with a skin-core structure.

5. The highly sensitive antibacterial composite leather according to claim 1, characterized in that: The preparation method of the polymer fiber cloth grey cloth loaded with a high molecular compound comprises: soaking a grey cloth woven from polymer fibers in a high molecular compound solution, and then solidifying and forming the grey cloth in a coagulation bath to obtain a polymer fiber cloth grey cloth loaded with a high molecular compound.

6. The highly sensitive antibacterial composite leather according to claim 4 or 5, characterized in that: The polymer complex solution contains salt ions; the salt ions include sodium ions or calcium ions, and the concentration of the salt ions in the polymer complex solution is 0.01~5mol / L; the pH value of the polymer complex solution is 1~5, and the concentration of the polymer complex in the polymer complex solution is 1~50wt.%.

7. The highly sensitive antibacterial composite leather according to claim 6, characterized in that: The coagulation bath contains auxiliary curing ions, which include one or more of sodium ions, calcium ions, iron ions and copper ions. The concentration of the auxiliary curing ions in the coagulation bath is 0.001-5 mol / L, and the pH value of the coagulation bath is 9-14.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the polymer complex functional phase to the polymer fiber structural phase is 1:100 to 100:

1.

9. The method for preparing the highly sensitive antibacterial composite leather according to any one of claims 1 to 8, characterized in that: The following steps are involved: The high molecular complex functional phase and the polymer fiber structural phase are compounded and post-processed to obtain a highly sensitive antibacterial composite leather.

10. Use of the highly sensitive antibacterial composite leather according to any one of claims 1 to 8 or the highly sensitive antibacterial composite leather prepared by the preparation method according to claim 9 in automobile interiors, medical devices or sports rehabilitation equipment.

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